Search results for: graphene nanosheets
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 389

Search results for: graphene nanosheets

89 The Impact of β Nucleating Agents and Carbon-Based Nanomaterials on Water Vapor Permeability of Polypropylene Composite Films

Authors: Glykeria A. Visvini, George Ν. Mathioudakis, Amaia Soto Beobide, George A. Voyiatzis

Abstract:

Polymer nanocomposites are materials in which a polymer matrix is reinforced with nanoscale inclusions, such as nanoparticles, nanoplates, or nanofibers. These nanoscale inclusions can significantly enhance the mechanical, thermal, electrical, and other properties of the polymer matrix, making them attractive for a wide range of industrial applications. These properties can be tailored by adjusting the type and the concentration of the nanoinclusions, which provides a high degree of flexibility in their design and development. An important property that polymeric membranes can exhibit is water vapor permeability (WVP). This can be accomplished by various methods, including the incorporation of micro/nano-fillers into the polymer matrix. In this way, a micro/nano-pore network can be formed, allowing water vapor to permeate through the membrane. At the same time, the membrane can be stretched uni- or bi-axially, creating aligned or cross-linked micropores in the composite, respectively, which can also increase the WVP. Nowadays, in industry, stretched films reinforced with CaCO3 develop micro-porosity sufficient to give them breathability characteristics. Carbon-based nanomaterials, such as graphene oxide (GO), are tentatively expected to be able to effectively improve the WVP of corresponding composite polymer films. The presence in the GO structure of various functional oxidizing groups enhances its ability to attract and channel water molecules, exploiting the unique large surface area of graphene that allows the rapid transport of water molecules. Polypropylene (PP) is widely used in various industrial applications due to its desirable properties, including good chemical resistance, excellent thermal stability, low cost, and easy processability. The specific properties of PP are highly influenced by its crystalline behavior, which is determined by its processing conditions. The development of the β-crystalline phase in PP, in combination with stretching, is anticipating improving the microporosity of the polymer matrix, thereby enhancing its WVP. The aim of present study is to create breathable PP composite membranes using carbon-based nanomaterials, such as graphene oxide (GO), reduced graphene oxide (rGO), and graphene nanoplatelets (GNPs). Unlike traditional methods that rely on the drawing process to enhance the WVP of PP, this study intents to develop a low-cost approach using melt mixing with β-nucleating agents and carbon fillers to create highly breathable PP composite membranes. The study aims to investigate how the concentration of these additives affects the water vapor transport properties of the resulting PP films/membranes. The presence of β-nucleating agents and carbon fillers is expected to enhance β-phase growth in PP, while an alternation between β- and α-phase is expected to lead to improved microporosity and WVP. Our ambition is to develop highly breathable PP composite films with superior performance and at a lower cost compared to the benchmark. Acknowledgment: This research has been co‐financed by the European Union and Greek national funds through the Operational Program Competitiveness, Entrepreneurship and Innovation, under the call «Special Actions "AQUACULTURE"-"INDUSTRIAL MATERIALS"-"OPEN INNOVATION IN CULTURE"» (project code: Τ6YBP-00337)

Keywords: carbon based nanomaterials, nanocomposites, nucleating agent, polypropylene, water vapor permeability

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88 The Toxicity of Doxorubicin Connected with Nanotransporters

Authors: Iva Blazkova, Amitava Moulick, Vedran Milosavljevic, Pavel Kopel, Marketa Vaculovicova, Vojtech Adam, Rene Kizek

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Doxorubicin is one of the most commonly used and the most effective chemotherapeutic drugs. This antracycline drug isolated from the bacteria Streptomyces peuceticus var. caesius is sold under the trade name Adriamycin (hydroxydaunomycin, hydroxydaunorubicin). Doxorubicin is used in single therapy to treat hematological malignancies (blood cancers, leukaemia, lymphoma), many types of carcinoma (solid tumors) and soft tissue sarcomas. It has many serious side effects like nausea and vomiting, hair lost, myelosupression, oral mucositis, skin reactions and redness, but the most serious one is the cardiotoxicity. Because of the risk of heart attack and congestive heart failure, the total dose administered to patients has to be accurately monitored. With the aim to lower the side effects and to targeted delivery of doxorubicin into the tumor tissue, the different nanoparticles are studied. The drug can be bound on a surface of nanoparticle, encapsulated in the inner cavity, or incorporated into the structure of nanoparticle. Among others, carbon nanoparticles (graphene, carbon nanotubes, fullerenes) are highly studied. Besides the number of inorganic nanoparticles, a great potential exhibit also organic ones mainly lipid-based and polymeric nanoparticle. The aim of this work was to perform a toxicity study of free doxorubicin compared to doxorubicin conjugated with various nanotransporters. The effect of liposomes, fullerenes, graphene, and carbon nanotubes on the toxicity was analyzed. As a first step, the binding efficacy of between doxorubicin and the nanotransporter was determined. The highest efficacy was detected in case of liposomes (85% of applied drug was encapsulated) followed by graphene, carbon nanotubes and fullerenes. For the toxicological studies, the chicken embryos incubated under controlled conditions (37.5 °C, 45% rH, rotation every 2 hours) were used. In 7th developmental day of chicken embryos doxorubicin or doxorubicin-nanotransporter complex was applied on the chorioallantoic membrane of the eggs and the viability was analyzed every day till the 17th developmental day. Then the embryos were extracted from the shell and the distribution of doxorubicin in the body was analyzed by measurement of organs extracts using laser induce fluorescence detection. The chicken embryo mortality caused by free doxorubicin (30%) was significantly lowered by using the conjugation with nanomaterials. The highest accumulation of doxorubicin and doxorubicin nanotransporter complexes was observed in the liver tissue

Keywords: doxorubicin, chicken embryos, nanotransporters, toxicity

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87 Finite Element Molecular Modeling: A Structural Method for Large Deformations

Authors: A. Rezaei, M. Huisman, W. Van Paepegem

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Atomic interactions in molecular systems are mainly studied by particle mechanics. Nevertheless, researches have also put on considerable effort to simulate them using continuum methods. In early 2000, simple equivalent finite element models have been developed to study the mechanical properties of carbon nanotubes and graphene in composite materials. Afterward, many researchers have employed similar structural simulation approaches to obtain mechanical properties of nanostructured materials, to simplify interface behavior of fiber-reinforced composites, and to simulate defects in carbon nanotubes or graphene sheets, etc. These structural approaches, however, are limited to small deformations due to complicated local rotational coordinates. This article proposes a method for the finite element simulation of molecular mechanics. For ease in addressing the approach, here it is called Structural Finite Element Molecular Modeling (SFEMM). SFEMM method improves the available structural approaches for large deformations, without using any rotational degrees of freedom. Moreover, the method simulates molecular conformation, which is a big advantage over the previous approaches. Technically, this method uses nonlinear multipoint constraints to simulate kinematics of the atomic multibody interactions. Only truss elements are employed, and the bond potentials are implemented through constitutive material models. Because the equilibrium bond- length, bond angles, and bond-torsion potential energies are intrinsic material parameters, the model is independent of initial strains or stresses. In this paper, the SFEMM method has been implemented in ABAQUS finite element software. The constraints and material behaviors are modeled through two Fortran subroutines. The method is verified for the bond-stretch, bond-angle and bond-torsion of carbon atoms. Furthermore, the capability of the method in the conformation simulation of molecular structures is demonstrated via a case study of a graphene sheet. Briefly, SFEMM builds up a framework that offers more flexible features over the conventional molecular finite element models, serving the structural relaxation modeling and large deformations without incorporating local rotational degrees of freedom. Potentially, the method is a big step towards comprehensive molecular modeling with finite element technique, and thereby concurrently coupling an atomistic domain to a solid continuum domain within a single finite element platform.

Keywords: finite element, large deformation, molecular mechanics, structural method

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86 Mitigating the Aggregation of Human Islet Amyloid Polypeptide with Nanomaterials

Authors: Ava Faridi, Pouya Faridi, Aleksandr Kakinen, Ibrahim Javed, Thomas P. Davis, Pu Chun Ke

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Human islet amyloid polypeptide (IAPP) is a hormone associated with glycemic control and type 2 diabetes. Biophysically, the chirality of IAPP fibrils has been little explored with respect to the aggregation and toxicity of the peptide. Biochemically, it remains unclear as for how protein expression in pancreatic beta cells may be altered by cell exposure to the peptide, and how such changes may be mitigated by nanoparticle inhibitors for IAPP aggregation. In this study, we first demonstrated the elimination of the IAPP nucleation phase and shortening of its elongation phase by silica nanoribbons. This accelerated IAPP fibrillization translated to reduced toxicity, especially for the right-handed silica nanoribbons, as revealed by cell viability, helium ion microscopy, as well as zebrafish embryo survival, developmental and behavioral assays. We then examined the proteomes of βTC6 pancreatic beta cells exposed to the three main aggregation states of monomeric, oligomeric and amyloid fibrillar IAPP, and compared that with cellular protein expression modulated by graphene quantum dots (GQDs). A total of 29 proteins were significantly regulated by different forms of IAPP, and the majority of these proteins were nucleotide-binding proteins. A regulatory capacity of GQDs against aberrant protein expression was confirmed. These studies have demonstrated the great potential of employing nanomaterials targeting the mesoscopic enantioselectivity and protein expression dysregulation in pancreatic beta cells.

Keywords: graphene quantum dots, IAPP, silica nanoribbons, protein expression, toxicity

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85 Microwave-Assisted Fabrication of Visible-Light Activated BiOBr-Nanoplate Photocatalyst

Authors: Meichen Lee, Michael K. H. Leung

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In recent years, visible-light activated photocatalysis has become a major field of intense researches for the higher efficiency of solar energy utilizations. Many attempts have been made on the modification of wide band gap semiconductors, while more and more efforts emphasize on cost-effective synthesis of visible-light activated catalysts. In this work, BiOBr nanoplates with band gap of visible-light range are synthesized through a promising microwave solvothermal method. The treatment time period and temperature dependent BiOBr nanosheets of various particle sizes are investigated through SEM. BiOBr synthesized under the condition of 160°C for 60 mins shows the most uniform particle sizes around 311 nm and the highest surface-to-volume ratio on account of its smallest average particle sizes compared with others. It exhibits the best photocatalytic behavior among all samples in RhB degradation.

Keywords: microwave solvothermal process, nanoplates, solar energy, visible-light photocatalysis

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84 A Facile Nanocomposite of Graphene Oxide Reinforced Chitosan/Poly-Nitroaniline Polymer as a Highly Efficient Adsorbent for Extracting Polycyclic Aromatic Hydrocarbons from Tea Samples

Authors: Adel M. Al-Shutairi, Ahmed H. Al-Zahrani

Abstract:

Tea is a popular beverage drunk by millions of people throughout the globe. Tea has considerable health advantages, in-cluding antioxidant, antibacterial, antiviral, chemopreventive, and anticarcinogenic properties. As a result of environmental pollution (atmospheric deposition) and the production process, tealeaves may also include a variety of dangerous substances, such as polycyclic aromatic hydrocarbons (PAHs). In this study, graphene oxide reinforced chitosan/poly-nitroaniline polymer was prepared to develop a sensitive and reliable solid phase extraction method (SPE) for extraction of PAH7 in tea samples, followed by high-performance liquid chromatography- fluorescence detection. The prepared adsorbent was validated in terms of linearity, the limit of detection, the limit of quantification, recovery (%), accuracy (%), and precision (%) for the determination of the PAH7 (benzo[a]pyrene, benzo[a]anthracene, benzo[b]fluoranthene, chrysene, benzo[b]fluoranthene, Dibenzo[a,h]anthracene and Benzo[g,h,i]perylene) in tea samples. The concentration was determined in two types of tea commercially available in Saudi Arabia, including black tea and green tea. The maximum mean of Σ7PAHs in black tea samples was 68.23 ± 0.02 ug kg-1 and 26.68 ± 0.01 ug kg-1 in green tea samples. The minimum mean of Σ7PAHs in black tea samples was 37.93 ± 0.01 ug kg-1 and 15.26 ± 0.01 ug kg-1 in green tea samples. The mean value of benzo[a]pyrene in black tea samples ranged from 6.85 to 12.17 ug kg-1, where two samples exceeded the standard level (10 ug kg-1) established by the European Union (UE), while in green tea ranged from 1.78 to 2.81 ug kg-1. Low levels of Σ7PAHs in green tea samples were detected in comparison with black tea samples.

Keywords: polycyclic aromatic hydrocarbons, CS, PNA and GO, black/green tea, solid phase extraction, Saudi Arabia

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83 Classic Modelled Hybrid Electric Vehicles Using The Power of Internet Of Things

Authors: Venkatesh Krishna Murthy

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The era before government-regulated automotive designs gave us some astonishing vehicles that are well worth to keep on the road. The fact that restoring an automobile in 2015 does not mean it will perform like one designed in 2021. This is one of the reasons that manufacturers continue to turn to vintage hardware for future enhancements in their vehicles. Now we need to understand that a modern chassis could possibly allow manufacturers to give vintage performance cars a level of braking capability, compatibility with tires, chassis rigidity, suspension sophistication, and steering response, an experience only racers got until now. However, half a century of advancements in engineering can have a great impact on design in any field, and the automotive realm which holds no exception. In the current situation, a growing number of companies offer chassis and braking components to onboard manufacturers to retrofit contemporary technology for their vintage vehicles to modernize them at the foundation level. The recent question arises on performance on lithium batteries, as opposed to simply bolting upgraded components, for ex. lithium batteries with graphene as superconductive material to enhance performance, an area deeply investigated. Serving as the “bones” of the vehicle, the chassis and frame play a central role in dictating how that automobile will perform. While the desire to maintain originality is alluring for many, the benefits of a modern chassis are vast. In some situations, it also allows builders to put cars back on the road that might otherwise be too far gone. “There’s a couple of different factors at play here – one of them being that these older cars from the ’40s, ’50s, and ’60s have seen a lot of weather and a lot of road miles over the years, more often than not,” says Craig Morrison of Art Morrison Enterprises.

Keywords: hybrid electric vehicles, internet of things, lithium graphene batteries, classic car chassis

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82 Polypyrrole as Bifunctional Materials for Advanced Li-S Batteries

Authors: Fang Li, Jiazhao Wang, Jianmin Ma

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The practical application of Li-S batteries is hampered due to poor cycling stability caused by electrolyte-dissolved lithium polysulfides. Dual functionalities such as strong chemical adsorption stability and high conductivity are highly desired for an ideal host material for a sulfur-based cathode. Polypyrrole (PPy), as a conductive polymer, was widely studied as matrixes for sulfur cathode due to its high conductivity and strong chemical interaction with soluble polysulfides. Thus, a novel cathode structure consisting of a free-standing sulfur-polypyrrole cathode and a polypyrrole coated separator was designed for flexible Li-S batteries. The PPy materials show strong interaction with dissoluble polysulfides, which could suppress the shuttle effect and improve the cycling stability. In addition, the synthesized PPy film with a rough surface acts as a current collector, which improves the adhesion of sulfur materials and restrain the volume expansion, enhancing the structural stability during the cycling process. For further enhancing the cycling stability, a PPy coated separator was also applied, which could make polysulfides into the cathode side to alleviate the shuttle effect. Moreover, the PPy layer coated on commercial separator is much lighter than other reported interlayers. A soft-packaged flexible Li-S battery has been designed and fabricated for testing the practical application of the designed cathode and separator, which could power a device consisting of 24 light-emitting diode (LED) lights. Moreover, the soft-packaged flexible battery can still show relatively stable cycling performance after repeated bending, indicating the potential application in flexible batteries. A novel vapor phase deposition method was also applied to prepare uniform polypyrrole layer coated sulfur/graphene aerogel composite. The polypyrrole layer simultaneously acts as host and adsorbent for efficient suppression of polysulfides dissolution through strong chemical interaction. The density functional theory (DFT) calculations reveal that the polypyrrole could trap lithium polysulfides through stronger bonding energy. In addition, the deflation of sulfur/graphene hydrogel during the vapor phase deposition process enhances the contact of sulfur with matrixes, resulting in high sulfur utilization and good rate capability. As a result, the synthesized polypyrrole coated sulfur/graphene aerogel composite delivers a specific discharge capacity of 1167 mAh g⁻¹ and 409.1 mAh g⁻¹ at 0.2 C and 5 C respectively. The capacity can maintain at 698 mAh g⁻¹ at 0.5 C after 500 cycles, showing an ultra-slow decay rate of 0.03% per cycle.

Keywords: polypyrrole, strong chemical interaction, long-term stability, Li-S batteries

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81 Facile Synthesis of Heterostructured Bi₂S₃-WS₂ Photocatalysts for Photodegradation of Organic Dye

Authors: S. V. Prabhakar Vattikuti, Chan Byon

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In this paper, we report a facile synthetic strategy of randomly disturbed Bi₂S₃ nanorods on WS₂ nanosheets, which are synthesized via a controlled hydrothermal method without surfactant under an inert atmosphere. We developed a simple hydrothermal method for the formation of heterostructured of Bi₂S₃/WS₂ with a large scale (>95%). The structural features, composition, and morphology were characterized by XRD, SEM-EDX, TEM, HRTEM, XPS, UV-vis spectroscopy, N₂ adsorption-desorption, and TG-DTA measurements. The heterostructured Bi₂S₃/WS₂ composite has significant photocatalytic efficiency toward the photodegradation of organic dye. The time-dependent UV-vis absorbance spectroscopy measurement was consistent with the enhanced photocatalytic degradation of rhodamine B (RhB) under visible light irradiation with the diminishing carrier recombination for the Bi₂S₃/WS₂ photocatalyst. Due to their marked synergistic effects, the supported Bi₂S₃ nanorods on WS₂ nanosheet heterostructures exhibit significant visible-light photocatalytic activity and stability for the degradation of RhB. A possible reaction mechanism is proposed for the Bi₂S₃/WS₂ composite.

Keywords: photocatalyst, heterostructures, transition metal disulfides, organic dye, nanorods

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80 Toxicity Evaluation of Reduced Graphene Oxide on First Larval Stages of Artemia sp.

Authors: Roberta Pecoraro

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The focus of this work was to investigate the potential toxic effect of titanium dioxide-reduced graphene oxide (TiO₂-rGO) nanocomposites on nauplii of microcrustacean Artemia sp. In order to assess the nanocomposite’s toxicity, a short-term test was performed by exposing nauplii to solutions containing TiO₂-rGO. To prepare titanium dioxide-reduced graphene oxide (TiO₂-rGO) nanocomposites, a green procedure based on solar photoreduction was proposed; it allows to obtain the photocatalysts by exploiting the photocatalytic properties of titania activated by the solar irradiation in order to avoid the high temperatures and pressures required for the standard hydrothermal synthesis. Powders of TiO₂-rGO supplied by the Department of Chemical Sciences (University of Catania) are indicated as TiO₂-rGO at 1% and TiO₂-rGO at 2%. Starting from a stock solution (1mg rGO-TiO₂/10 ml ASPM water) of each type, we tested four different concentrations (serial dilutions ranging from 10⁻¹ to 10⁻⁴ mg/ml). All the solutions have been sonicated for 12 min prior to use. Artificial seawater (called ASPM water) was prepared to guarantee the hatching of the cysts and to maintain nauplii; the durable cysts used in this study, marketed by JBL (JBL GmbH & Co. KG, Germany), were hydrated with ASPM water to obtain nauplii (instar II-III larvae). The hatching of the cysts was carried out in the laboratory by immersing them in ASPM water inside a 500 ml beaker and keeping them constantly oxygenated thanks to an aerator for the insufflation of microbubble air: after 24-48 hours, the cysts hatched, and the nauplii appeared. The nauplii in the second and third stages of development were collected one-to-one, using stereomicroscopes, and transferred into 96-well microplates where one nauplius per well was added. The wells quickly have been filled with 300 µl of each specific concentration of the solution used, and control samples were incubated only with ASPM water. Replication was performed for each concentration. Finally, the microplates were placed on an orbital shaker, and the tests were read after 24 and 48 hours from inoculating the solutions to assess the endpoint (immobility/death) for the larvae. Nauplii that appeared motionless were counted as dead, and the percentages of mortality were calculated for each treatment. The results showed a low percentage of immobilization both for TiO₂-rGO at 1% and TiO₂-rGO at 2% for all concentrations tested: for TiO₂-rGO at 1% was below 12% after 24h and below 15% after 48h; for TiO₂-rGO at 2% was below 8% after 24h and below 12% after 48h. According to other studies in the literature, the results have not shown mortality nor toxic effects on the development of larvae after exposure to rGO. Finally, it is important to highlight that the TiO₂-rGO catalysts were tested in the solar photodegradation of a toxic herbicide (2,4-Dichlorophenoxyacetic acid, 2,4-D), obtaining a high percentage of degradation; therefore, this alternative approach could be considered a good strategy to obtain performing photocatalysts.

Keywords: Nauplii, photocatalytic properties, reduced GO, short-term toxicity test, titanium dioxide

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79 Advanced Lithium Recovery from Brine: 2D-Based Ion Selectivity Membranes

Authors: Nour S. Abdelrahman, Seunghyun Hong, Hassan A. Arafat, Daniel Choi, Faisal Al Marzooqi

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Abstract—The advancement of lithium extraction methods from water sources, particularly saltwater brine, is gaining prominence in the lithium recovery industry due to its cost-effectiveness. Traditional techniques like recrystallization, chemical precipitation, and solvent extraction for metal recovery from seawater or brine are energy-intensive and exhibit low efficiency. Moreover, the extensive use of organic solvents poses environmental concerns. As a result, there's a growing demand for environmentally friendly lithium recovery methods. Membrane-based separation technology has emerged as a promising alternative, offering high energy efficiency and ease of continuous operation. In our study, we explored the potential of lithium-selective sieve channels constructed from layers of 2D graphene oxide and MXene (transition metal carbides and nitrides), integrated with surface – SO₃₋ groups. The arrangement of these 2D sheets creates interplanar spacing ranging from 0.3 to 0.8 nm, which forms a barrier against multivalent ions while facilitating lithium-ion movement through nano capillaries. The introduction of the sulfonate group provides an effective pathway for Li⁺ ions, with a calculated binding energy of Li⁺ – SO³⁻ at – 0.77 eV, the lowest among monovalent species. These modified membranes demonstrated remarkably rapid transport of Li⁺ ions, efficiently distinguishing them from other monovalent and divalent species. This selectivity is achieved through a combination of size exclusion and varying binding affinities. The graphene oxide channels in these membranes showed exceptional inter-cation selectivity, with a Li⁺/Mg²⁺ selectivity ratio exceeding 104, surpassing commercial membranes. Additionally, these membranes achieved over 94% rejection of MgCl₂.

Keywords: ion permeation, lithium extraction, membrane-based separation, nanotechnology

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78 Electrical Investigations of Polyaniline/Graphitic Carbon Nitride Composites Using Broadband Dielectric Spectroscopy

Authors: M. A. Moussa, M. H. Abdel Rehim, G.M. Turky

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Polyaniline composites with carbon nitride, to overcome compatibility restriction with graphene, were prepared with the solution method. FTIR and Uv-vis spectra were used for structural conformation. While XRD and XPS confirmed the structures in addition to estimation of nitrogen atom surroundings, the pore sizes and the active surface area were determined from BET adsorption isotherm. The electrical and dielectric parameters were measured and calculated with BDS .

Keywords: carbon nitride, dynamic relaxation, electrical conductivity, polyaniline

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77 Various Shaped ZnO and ZnO/Graphene Oxide Nanocomposites and Their Use in Water Splitting Reaction

Authors: Sundaram Chandrasekaran, Seung Hyun Hur

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Exploring strategies for oxygen vacancy engineering under mild conditions and understanding the relationship between dislocations and photoelectrochemical (PEC) cell performance are challenging issues for designing high performance PEC devices. Therefore, it is very important to understand that how the oxygen vacancies (VO) or other defect states affect the performance of the photocatalyst in photoelectric transfer. So far, it has been found that defects in nano or micro crystals can have two possible significances on the PEC performance. Firstly, an electron-hole pair produced at the interface of photoelectrode and electrolyte can recombine at the defect centers under illumination of light, thereby reducing the PEC performances. On the other hand, the defects could lead to a higher light absorption in the longer wavelength region and may act as energy centers for the water splitting reaction that can improve the PEC performances. Even if the dislocation growth of ZnO has been verified by the full density functional theory (DFT) calculations and local density approximation calculations (LDA), it requires further studies to correlate the structures of ZnO and PEC performances. Exploring the hybrid structures composed of graphene oxide (GO) and ZnO nanostructures offer not only the vision of how the complex structure form from a simple starting materials but also the tools to improve PEC performances by understanding the underlying mechanisms of mutual interactions. As there are few studies for the ZnO growth with other materials and the growth mechanism in those cases has not been clearly explored yet, it is very important to understand the fundamental growth process of nanomaterials with the specific materials, so that rational and controllable syntheses of efficient ZnO-based hybrid materials can be designed to prepare nanostructures that can exhibit significant PEC performances. Herein, we fabricated various ZnO nanostructures such as hollow sphere, bucky bowl, nanorod and triangle, investigated their pH dependent growth mechanism, and correlated the PEC performances with them. Especially, the origin of well-controlled dislocation-driven growth and its transformation mechanism of ZnO nanorods to triangles on the GO surface were discussed in detail. Surprisingly, the addition of GO during the synthesis process not only tunes the morphology of ZnO nanocrystals and also creates more oxygen vacancies (oxygen defects) in the lattice of ZnO, which obviously suggest that the oxygen vacancies be created by the redox reaction between GO and ZnO in which the surface oxygen is extracted from the surface of ZnO by the functional groups of GO. On the basis of our experimental and theoretical analysis, the detailed mechanism for the formation of specific structural shapes and oxygen vacancies via dislocation, and its impact in PEC performances are explored. In water splitting performance, the maximum photocurrent density of GO-ZnO triangles was 1.517mA/cm-2 (under UV light ~ 360 nm) vs. RHE with high incident photon to current conversion Efficiency (IPCE) of 10.41%, which is the highest among all samples fabricated in this study and also one of the highest IPCE reported so far obtained from GO-ZnO triangular shaped photocatalyst.

Keywords: dislocation driven growth, zinc oxide, graphene oxide, water splitting

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76 Sustainable Membranes Based on 2D Materials for H₂ Separation and Purification

Authors: Juan A. G. Carrio, Prasad Talluri, Sergio G. Echeverrigaray, Antonio H. Castro Neto

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Hydrogen as a fuel and environmentally pleasant energy carrier is part of this transition towards low-carbon systems. The extensive deployment of hydrogen production, purification and transport infrastructures still represents significant challenges. Independent of the production process, the hydrogen generally is mixed with light hydrocarbons and other undesirable gases that need to be removed to obtain H₂ with the required purity for end applications. In this context, membranes are one of the simplest, most attractive, sustainable, and performant technologies enabling hydrogen separation and purification. They demonstrate high separation efficiencies and low energy consumption levels in operation, which is a significant leap compared to current energy-intensive options technologies. The unique characteristics of 2D laminates have given rise to a diversity of research on their potential applications in separation systems. Specifically, it is already known in the scientific literature that graphene oxide-based membranes present the highest reported selectivity of H₂ over other gases. This work explores the potential of a new type of 2D materials-based membranes in separating H₂ from CO₂ and CH₄. We have developed nanostructured composites based on 2D materials that have been applied in the fabrication of membranes to maximise H₂ selectivity and permeability, for different gas mixtures, by adjusting the membranes' characteristics. Our proprietary technology does not depend on specific porous substrates, which allows its integration in diverse separation modules with different geometries and configurations, looking to address the technical performance required for industrial applications and economic viability. The tuning and precise control of the processing parameters allowed us to control the thicknesses of the membranes below 100 nanometres to provide high permeabilities. Our results for the selectivity of new nanostructured 2D materials-based membranes are in the range of the performance reported in the available literature around 2D materials (such as graphene oxide) applied to hydrogen purification, which validates their use as one of the most promising next-generation hydrogen separation and purification solutions.

Keywords: membranes, 2D materials, hydrogen purification, nanocomposites

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75 Graphene Supported Nano Cerium Oxides Hybrid as an Electrocatalyst for Oxygen Reduction Reactions

Authors: Siba Soren, Purnendu Parhi

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Today, the world is facing a severe challenge due to depletion of traditional fossil fuels. Scientists across the globe are working for a solution that involves a dramatic shift to practical and environmentally sustainable energy sources. High-capacity energy systems, such as metal-air batteries, fuel cells, are highly desirable to meet the urgent requirement of sustainable energies. Among the fuel cells, Direct methanol fuel cells (DMFCs) are recognized as an ideal power source for mobile applications and have received considerable attention in recent past. In this advanced electrochemical energy conversion technologies, Oxygen Reduction Reaction (ORR) is of utmost importance. However, the poor kinetics of cathodic ORR in DMFCs significantly hampers their possibilities of commercialization. The oxygen is reduced in alkaline medium either through a 4-electron (equation i) or a 2-electron (equation ii) reduction pathway at the cathode ((i) O₂ + 2H₂O + 4e⁻ → 4OH⁻, (ii) O₂ + H₂O + 2e⁻ → OH⁻ + HO₂⁻ ). Due to sluggish ORR kinetics the ability to control the reduction of molecular oxygen electrocatalytically is still limited. The electrocatalytic ORR starts with adsorption of O₂ on the electrode surface followed by O–O bond activation/cleavage and oxide removal. The reaction further involves transfer of 4 electrons and 4 protons. The sluggish kinetics of ORR, on the one hand, demands high loading of precious metal-containing catalysts (e.g., Pt), which unfavorably increases the cost of these electrochemical energy conversion devices. Therefore, synthesis of active electrocatalyst with an increase in ORR performance is need of the hour. In the recent literature, there are many reports on transition metal oxide (TMO) based ORR catalysts for their high activity TMOs are also having drawbacks like low electrical conductivity, which seriously affects the electron transfer process during ORR. It was found that 2D graphene layer is having high electrical conductivity, large surface area, and excellent chemical stability, appeared to be an ultimate choice as support material to enhance the catalytic performance of bare metal oxide. g-C₃N₄ is also another candidate that has been used by the researcher for improving the ORR performance of metal oxides. This material provides more active reaction sites than other N containing carbon materials. Rare earth oxide like CeO₂ is also a good candidate for studying the ORR activity as the metal oxide not only possess unique electronic properties but also possess catalytically active sites. Here we will discuss the ORR performance (in alkaline medium) of N-rGO/C₃N₄ supported nano Cerium Oxides hybrid synthesized by microwave assisted Solvothermal method. These materials exhibit superior electrochemical stability and methanol tolerance capability to that of commercial Pt/C.

Keywords: oxygen reduction reaction, electrocatalyst, cerium oxide, graphene

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74 Nanoscale Metal-Organic Framework Coated Carbon Nitride Nanosheet for Combination Cancer Therapy

Authors: Rui Chen, Jinfeng Zhang, Chun-Sing Lee

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In the past couple of decades, nanoscale metal-organic frameworks (NMOFs) have been highlighted as promising delivery platforms for biomedical applications, which combine many potent features such as high loading capacity, progressive biodegradability and low cytotoxicity. While NMOF has been extensively used as carriers for drugs of different modalities, so far there is no report on exploiting the advantages of NMOF for combination therapy. Herein, we prepared core-shell nanoparticles, where each nanoparticle contains a single graphitic-phase carbon nitride (g-C3N4) nanosheet encapsulated by a zeolitic-imidazolate frameworks-8 (ZIF-8) shell. The g-C3N4 nanosheets are effective visible-light photosensitizer for photodynamic therapy (PDT). When hosting DOX (doxorubicin), the as-synthesized core-shell nanoparticles could realize combinational photo-chemo therapy and provide dual-color fluorescence imaging. Therefore, we expect NMOFs-based core-shell nanoparticles could provide a new way to achieve much-enhanced cancer therapy.

Keywords: carbon nitride, combination therapy, drug delivery, nanoscale metal-organic frameworks

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73 Nanomaterials Based Biosensing Chip for Non-Invasive Detection of Oral Cancer

Authors: Suveen Kumar

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Oral cancer (OC) is the sixth most death causing cancer in world which includes tumour of lips, floor of the mouth, tongue, palate, cheeks, sinuses, throat, etc. Conventionally, the techniques used for OC detection are toluidine blue staining, biopsy, liquid-based cytology, visual attachments, etc., however these are limited by their highly invasive nature, low sensitivity, time consumption, sophisticated instrument handling, sample processing and high cost. Therefore, we developed biosensing chips for non-invasive detection of OC via CYFRA-21-1 biomarker. CYFRA-21-1 (molecular weight: 40 kDa) is secreted in saliva of OC patients which is a non-invasive biological fluid with a cut-off value of 3.8 ng mL-1, above which the subjects will be suffering from oral cancer. Therefore, in first work, 3-aminopropyl triethoxy silane (APTES) functionalized zirconia (ZrO2) nanoparticles (APTES/nZrO2) were used to successfully detect CYFRA-21-1 in a linear detection range (LDR) of 2-16 ng mL-1 with sensitivity of 2.2 µA mL ng-1. Successively, APTES/nZrO2-RGO was employed to prevent agglomeration of ZrO2 by providing high surface area reduced graphene oxide (RGO) support and much wider LDR (2-22 ng mL-1) was obtained with remarkable limit of detection (LOD) as 0.12 ng mL-1. Further, APTES/nY2O3/ITO platform was used for oral cancer bioseneor development. The developed biosensor (BSA/anti-CYFRA-21-1/APTES/nY2O3/ITO) have wider LDR (0.01-50 ng mL-1) with remarkable limit of detection (LOD) as 0.01 ng mL-1. To improve the sensitivity of the biosensing platform, nanocomposite of yattria stabilized nanostructured zirconia-reduced graphene oxide (nYZR) based biosensor has been developed. The developed biosensing chip having ability to detect CYFRA-21-1 biomolecules in the range of 0.01-50 ng mL-1, LOD of 7.2 pg mL-1 with sensitivity of 200 µA mL ng-1. Further, the applicability of the fabricated biosensing chips were also checked through real sample (saliva) analysis of OC patients and the obtained results showed good correlation with the standard protein detection enzyme linked immunosorbent assay (ELISA) technique.

Keywords: non-invasive, oral cancer, nanomaterials, biosensor, biochip

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72 Preparation of 1D Nano-Polyaniline/Dendritic Silver Composites

Authors: Wen-Bin Liau, Wan-Ting Wang, Chiang-Jen Hsiao, Sheng-Mao Tseng

Abstract:

In this paper, an interesting and easy method to prepare one-dimensional nanostructured polyaniline/dendritic silver composites is reported. It is well known that the morphology of metal particle is a very important factor to influence the properties of polymer-metal composites. Usually, the dendritic silver is prepared by kinetic control in reduction reaction. It is not a thermodynamically stable structure. It is the goal to reduce silver ion to dendritic silver by polyaniline polymer via kinetic control and form one-dimensional nanostructured polyaniline/dendritic silver composites. The preparation is a two steps sequential reaction. First step, the polyaniline networks composed of nano fibrillar polyaniline are synthesized from aniline monomers aqueous with ammonium persulfate as the initiator at room temperature. In second step, the silver nitrate is added into polyaniline networks dispersed in deionized water. The dendritic silver is formed via reduction by polyaniline networks under the kinetic control. The formation of polyaniline is discussed via transmission electron microscopy (TEM). Nanosheets, nanotubes, nanospheres, nanosticks, and networks are observed via TEM. Then, the mechanism of formation of one-dimensional nanostructured polyaniline/dendritic silver composites is discussed. The formation of dendritic silver is observed by TEM and X-ray diffraction.

Keywords: 1D nanostructured polyaniline, dendritic silver, synthesis

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71 Hydrothermally Fabricated 3-D Nanostructure Metal Oxide Sensors

Authors: Mohammad Alenezi

Abstract:

Hierarchical nanostructures with higher dimensionality, consisting of nanostructure building blocks such as nanowires, nanotubes, or nanosheets are very attractive. They hold great properties like the high surface-to-volume ratio and well-ordered porous structures, which can be very challenging to attain for other mono-morphological nanostructures. Well-ordered hierarchical nanostructures with high surface-to-volume ratios facilitate gas diffusion into their surfaces as well as scattering of light. Therefore, hierarchical nanostructures are expected to perform highly as gas sensors. A multistage controlled hydrothermal synthesis method to fabricate high-performance single ZnO brushlike hierarchical nanostructure gas sensor from initial nanowires is reported. The performance of the sensor based on brush-like hierarchical nanostructure is analyzed and compared to that of a nanowire gas sensor. The hierarchical gas sensor demonstrated high sensitivity toward low concentration of acetone at high speed of response. The enhancement in the hierarchical sensor performance is attributed to the increased surface to volume ratio, reduction in dimensionality of the nanowire building blocks, formation of junctions between the initial nanowire and the secondary nanowires, and enhanced gas diffusion into the surfaces of the hierarchical nanostructures.

Keywords: metal oxide, nanostructure, hydrothermal, sensor

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70 Atomic Scale Storage Mechanism Study of the Advanced Anode Materials for Lithium-Ion Batteries

Authors: Xi Wang, Yoshio Bando

Abstract:

Lithium-ion batteries (LIBs) can deliver high levels of energy storage density and offer long operating lifetimes, but their power density is too low for many important applications. Therefore, we developed some new strategies and fabricated novel electrodes for fast Li transport and its facile synthesis including N-doped graphene-SnO2 sandwich papers, bicontinuous nanoporous Cu/Li4Ti5O12 electrode, and binder-free N-doped graphene papers. In addition, by using advanced in-TEM, STEM techniques and the theoretical simulations, we systematically studied and understood their storage mechanisms at the atomic scale, which shed a new light on the reasons of the ultrafast lithium storage property and high capacity for these advanced anodes. For example, by using advanced in-situ TEM, we directly investigated these processes using an individual CuO nanowire anode and constructed a LIB prototype within a TEM. Being promising candidates for anodes in lithium-ion batteries (LIBs), transition metal oxide anodes utilizing the so-called conversion mechanism principle typically suffer from the severe capacity fading during the 1st cycle of lithiation–delithiation. Also we report on the atomistic insights of the GN energy storage as revealed by in situ TEM. The lithiation process on edges and basal planes is directly visualized, the pyrrolic N "hole" defect and the perturbed solid-electrolyte-interface (SEI) configurations are observed, and charge transfer states for three N-existing forms are also investigated. In situ HRTEM experiments together with theoretical calculations provide a solid evidence that enlarged edge {0001} spacings and surface "hole" defects result in improved surface capacitive effects and thus high rate capability and the high capacity is owing to short-distance orderings at the edges during discharging and numerous surface defects; the phenomena cannot be understood previously by standard electron or X-ray diffraction analyses.

Keywords: in-situ TEM, STEM, advanced anode, lithium-ion batteries, storage mechanism

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69 Development of Calcium Carbonate Molecular Sheets via Wet Chemical Route

Authors: Sudhir Kumar Sharma, Ramesh Jagannathan

Abstract:

The interaction of organic and inorganic matrices of biological origin resulting in self-assembled structures with unique properties is well established. The development of such self-assembled nanostructures by synthetic and bio-inspired techniques is an established field of active research. Among bio-materials, nacre, a laminar stack of calcium carbonate nanosheets, which are interleaved with organic material, has long been focused research due to its unique mechanical properties. In this paper, we present the development of nacre-like lamellar structures made up of calcium carbonate via a wet chemical route. We used the binding affinity of carboxylate anions and calcium cations using poly (acrylic) acid (PAA) to lead CaCO₃ crystallization. In these experiments, we selected calcium acetate as the precursor molecule along with PAA (Mw ~ 8000 Da). We found that Ca⁺²/COO⁻ ratio provided a tunable control for the morphology and growth of CaCO₃ nanostructures. Drop casting one such formulation on a silicon substrate followed by calcination resulted in co-planner, molecular sheets of CaCO₃, separated by a spacer layer of carbon. The scope of our process could be expanded to produce unit cell thick molecular sheets of other important inorganic materials.

Keywords: self-assembled structures, bio-inspired materials, calcium carbonate, wet chemical route

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68 Novel Anticorrosion Epoxy Reinforced Graphitic Nanocomposite as a Durable Surface

Authors: Shimaa A. Higazy, Mohamed S. Selim, Olfat E. El-Azabawy, Abeer A. Hassan

Abstract:

We designed novel epoxy/graphitic carbon nitride (g-C₃N₄) nanocomposite materials as suitable surface coatings. g-C₃N₄ nanosheets were facilely prepared and dispersed in the epoxy resin via solution casting. This research focuses on the mechanical and anticorrosion properties of g-C₃N₄ nanofiller reinforced epoxy nanocomposites. The structures, sizes, and morphologies of designed polymeric nanocomposites and nanofillers were elucidated using various techniques such as FT-IR, NMR, FE-TEM, FE-SEM. The developed nanocomposite was applied as a surface coating by air-assisted spray method. The structure-property relationship was studied for different concentrations of nanofiller in the epoxy matrix. The anticorrosive properties were studied via electrochemical experiments, including potentiodynamic polarization, electrochemical impedance, and open-circuit potential analyses, as well as salt spray test. Mechanical durability was assessed by various methods, such as impact, T-bending, and crosscut tests. Surface heterogeneity, elasticity, and corrosion-resistance features are among the merits of developed composite. The highest improvement was achieved with well dispersion of g-C₃N₄ sheets fillers. This fascinating epoxy nanostructured coating provides a promising anticorrosive coatings for a sustainable future environment.

Keywords: epoxy, nanocomposite, surface coating, anticorrosive properties, mechanical durability

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67 New Technique of Estimation of Charge Carrier Density of Nanomaterials from Thermionic Emission Data

Authors: Dilip K. De, Olukunle C. Olawole, Emmanuel S. Joel, Moses Emetere

Abstract:

A good number of electronic properties such as electrical and thermal conductivities depend on charge carrier densities of nanomaterials. By controlling the charge carrier densities during the fabrication (or growth) processes, the physical properties can be tuned. In this paper, we discuss a new technique of estimating the charge carrier densities of nanomaterials from the thermionic emission data using the newly modified Richardson-Dushman equation. We find that the technique yields excellent results for graphene and carbon nanotube.

Keywords: charge carrier density, nano materials, new technique, thermionic emission

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66 High Photosensitivity and Broad Spectral Response of Multi-Layered Germanium Sulfide Transistors

Authors: Rajesh Kumar Ulaganathan, Yi-Ying Lu, Chia-Jung Kuo, Srinivasa Reddy Tamalampudi, Raman Sankar, Fang Cheng Chou, Yit-Tsong Chen

Abstract:

In this paper, we report the optoelectronic properties of multi-layered GeS nanosheets (~28 nm thick)-based field-effect transistors (called GeS-FETs). The multi-layered GeS-FETs exhibit remarkably high photoresponsivity of Rλ ~ 206 AW-1 under illumination of 1.5 µW/cm2 at  = 633 nm, Vg = 0 V, and Vds = 10 V. The obtained Rλ ~ 206 AW-1 is excellent as compared with a GeS nanoribbon-based and the other family members of group IV-VI-based photodetectors in the two-dimensional (2D) realm, such as GeSe and SnS2. The gate-dependent photoresponsivity of GeS-FETs was further measured to be able to reach Rλ ~ 655 AW-1 operated at Vg = -80 V. Moreover, the multi-layered GeS photodetector holds high external quantum efficiency (EQE ~ 4.0 × 104 %) and specific detectivity (D* ~ 2.35 × 1013 Jones). The measured D* is comparable to those of the advanced commercial Si- and InGaAs-based photodiodes. The GeS photodetector also shows an excellent long-term photoswitching stability with a response time of ~7 ms over a long period of operation (>1 h). These extraordinary properties of high photocurrent generation, broad spectral range, fast response, and long-term stability make the GeS-FET photodetector a highly qualified candidate for future optoelectronic applications.

Keywords: germanium sulfide, photodetector, photoresponsivity, external quantum efficiency, specific detectivity

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65 Thermal Analysis of Automobile Radiator Using Nanofluids

Authors: S. Sumanth, Babu Rao Ponangi, K. N. Seetharamu

Abstract:

As the technology is emerging day by day, there is a need for some better methodology which will enhance the performance of radiator. Nanofluid is the one area which has promised the enhancement of the radiator performance. Currently, nanofluid has got a well effective solution for enhancing the performance of the automobile radiators. Suspending the nano sized particle in the base fluid, which has got better thermal conductivity value when compared to a base fluid, is preferably considered for nanofluid. In the current work, at first mathematical formulation has been carried out, which will govern the performance of the radiator. Current work is justified by plotting the graph for different parameters. Current work justifies the enhancement of radiator performance using nanofluid.

Keywords: nanofluid, radiator performance, graphene, gamma aluminium oxide (γ-Al2O3), titanium dioxide (TiO2)

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64 Studying the Dynamical Response of Nano-Microelectromechanical Devices for Nanomechanical Testing of Nanostructures

Authors: Mohammad Reza Zamani Kouhpanji

Abstract:

Characterizing the fatigue and fracture properties of nanostructures is one of the most challenging tasks in nanoscience and nanotechnology due to lack of a MEMS/NEMS device for generating uniform cyclic loadings at high frequencies. Here, the dynamic response of a recently proposed MEMS/NEMS device under different inputs signals is completely investigated. This MEMS/NEMS device is designed and modeled based on the electromagnetic force induced between paired parallel wires carrying electrical currents, known as Ampere’s Force Law (AFL). Since this MEMS/NEMS device only uses two paired wires for actuation part and sensing part, it represents highly sensitive and linear response for nanostructures with any stiffness and shapes (single or arrays of nanowires, nanotubes, nanosheets or nanowalls). In addition to studying the maximum gains at different resonance frequencies of the MEMS/NEMS device, its dynamical responses are investigated for different inputs and nanostructure properties to demonstrate the capability, usability, and reliability of the device for wide range of nanostructures. This MEMS/NEMS device can be readily integrated into SEM/TEM instruments to provide real time study of the fatigue and fracture properties of nanostructures as well as their softening or hardening behaviors, and initiation and/or propagation of nanocracks in them.

Keywords: MEMS/NEMS devices, paired wire actuators and sensors, dynamical response, fatigue and fracture characterization, Ampere’s force law

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63 Synthesis of High-Antifouling Ultrafiltration Polysulfone Membranes Incorporating Low Concentrations of Graphene Oxide

Authors: Abdulqader Alkhouzaam, Hazim Qiblawey, Majeda Khraisheh

Abstract:

Membrane treatment for desalination and wastewater treatment is one of the promising solutions to affordable clean water. It is a developing technology throughout the world and considered as the most effective and economical method available. However, the limitations of membranes’ mechanical and chemical properties restrict their industrial applications. Hence, developing novel membranes was the focus of most studies in the water treatment and desalination sector to find new materials that can improve the separation efficiency while reducing membrane fouling, which is the most important challenge in this field. Graphene oxide (GO) is one of the materials that have been recently investigated in the membrane water treatment sector. In this work, ultrafiltration polysulfone (PSF) membranes with high antifouling properties were synthesized by incorporating different loadings of GO. High-oxidation degree GO had been synthesized using a modified Hummers' method. The synthesized GO was characterized using different analytical techniques including elemental analysis, Fourier transform infrared spectroscopy - universal attenuated total reflectance sensor (FTIR-UATR), Raman spectroscopy, and CHNSO elemental analysis. CHNSO analysis showed a high oxidation degree of GO represented by its oxygen content (50 wt.%). Then, ultrafiltration PSF membranes incorporating GO were fabricated using the phase inversion technique. The prepared membranes were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM) and showed a clear effect of GO on PSF physical structure and morphology. The water contact angle of the membranes was measured and showed better hydrophilicity of GO membranes compared to pure PSF caused by the hydrophilic nature of GO. Separation properties of the prepared membranes were investigated using a cross-flow membrane system. Antifouling properties were studied using bovine serum albumin (BSA) and humic acid (HA) as model foulants. It has been found that GO-based membranes exhibit higher antifouling properties compared to pure PSF. When using BSA, the flux recovery ratio (FRR %) increased from 65.4 ± 0.9 % for pure PSF to 84.0 ± 1.0 % with a loading of 0.05 wt.% GO in PSF. When using HA as model foulant, FRR increased from 87.8 ± 0.6 % to 93.1 ± 1.1 % with 0.02 wt.% of GO in PSF. The pure water permeability (PWP) decreased with loadings of GO from 181.7 L.m⁻².h⁻¹.bar⁻¹ of pure PSF to 181.1, and 157.6 L.m⁻².h⁻¹.bar⁻¹ with 0.02 and 0.05 wt.% GO respectively. It can be concluded from the obtained results that incorporating low loading of GO could enhance the antifouling properties of PSF hence improving its lifetime and reuse.

Keywords: antifouling properties, GO based membranes, hydrophilicity, polysulfone, ultrafiltration

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62 Membranes for Direct Lithium Extraction (DLE)

Authors: Amir Razmjou, Elika Karbassi Yazdi

Abstract:

Several direct lithium extraction (DLE) technologies have been developed for Li extraction from different brines. Although laboratory studies showed that they can technically recover Li to 90%, challenges still remain in developing a sustainable process that can serve as a foundation for the lithium dependent low-carbon economy. There is a continuing quest for DLE technologies that do not need extensive pre-treatments, fewer materials, and have simplified extraction processes with high Li selectivity. Here, an overview of DLE technologies will be provided with an emphasis on the basic principles of the materials’ design for the development of membranes with nanochannels and nanopores with Li ion selectivity. We have used a variety of building blocks such as nano-clay, organic frameworks, Graphene/oxide, MXene, etc., to fabricate the membranes. Molecular dynamic simulation (MD) and density functional theory (DFT) were used to reveal new mechanisms by which high Li selectivity was obtained.

Keywords: lithium recovery, membrane, lithium selectivity, decarbonization

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61 Evaluation of Electrophoretic and Electrospray Deposition Methods for Preparing Graphene and Activated Carbon Modified Nano-Fibre Electrodes for Hydrogen/Vanadium Flow Batteries and Supercapacitors

Authors: Barun Chakrabarti, Evangelos Kalamaras, Vladimir Yufit, Xinhua Liu, Billy Wu, Nigel Brandon, C. T. John Low

Abstract:

In this work, we perform electrophoretic deposition of activated carbon on a number of substrates to prepare symmetrical coin cells for supercapacitor applications. From several recipes that involve the evaluation of a few solvents such as isopropyl alcohol, N-Methyl-2-pyrrolidone (NMP), or acetone to binders such as polyvinylidene fluoride (PVDF) and charging agents such as magnesium chloride, we display a working means for achieving supercapacitors that can achieve 100 F/g in a consistent manner. We then adapt this EPD method to deposit reduced graphene oxide on SGL 10AA carbon paper to achieve cathodic materials for testing in a hydrogen/vanadium flow battery. In addition, a self-supported hierarchical carbon nano-fibre is prepared by means of electrospray deposition of an iron phthalocyanine solution onto a temporary substrate followed by carbonisation to remove heteroatoms. This process also induces a degree of nitrogen doping on the carbon nano-fibres (CNFs), which allows its catalytic performance to improve significantly as detailed in other publications. The CNFs are then used as catalysts by attaching them to graphite felt electrodes facing the membrane inside an all-vanadium flow battery (Scribner cell using serpentine flow distribution channels) and efficiencies as high as 60% is noted at high current densities of 150 mA/cm². About 20 charge and discharge cycling show that the CNF catalysts consistently perform better than pristine graphite felt electrodes. Following this, we also test the CNF as an electro-catalyst in the hydrogen/vanadium flow battery (cathodic side as mentioned briefly in the first paragraph) facing the membrane, based upon past studies from our group. Once again, we note consistently good efficiencies of 85% and above for CNF modified graphite felt electrodes in comparison to 60% for pristine felts at low current density of 50 mA/cm² (this reports 20 charge and discharge cycles of the battery). From this preliminary investigation, we conclude that the CNFs may be used as catalysts for other systems such as vanadium/manganese, manganese/manganese and manganese/hydrogen flow batteries in the future. We are generating data for such systems at present, and further publications are expected.

Keywords: electrospinning, carbon nano-fibres, all-vanadium redox flow battery, hydrogen-vanadium fuel cell, electrocatalysis

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60 Photophysics of a Coumarin Molecule in Graphene Oxide Containing Reverse Micelle

Authors: Aloke Bapli, Debabrata Seth

Abstract:

Graphene oxide (GO) is the two-dimensional (2D) nanoscale allotrope of carbon having several physiochemical properties such as high mechanical strength, high surface area, strong thermal and electrical conductivity makes it an important candidate in various modern applications such as drug delivery, supercapacitors, sensors etc. GO has been used in the photothermal treatment of cancers and Alzheimer’s disease etc. The main idea to choose GO in our work is that it is a surface active molecule, it has a large number of hydrophilic functional groups such as carboxylic acid, hydroxyl, epoxide on its surface and in basal plane. So it can easily interact with organic fluorophores through hydrogen bonding or any other kind of interaction and easily modulate the photophysics of the probe molecules. We have used different spectroscopic techniques for our work. The Ground-state absorption spectra and steady-state fluorescence emission spectra were measured by using UV-Vis spectrophotometer from Shimadzu (model-UV-2550) and spectrofluorometer from Horiba Jobin Yvon (model-Fluoromax 4P) respectively. All the fluorescence lifetime and anisotropy decays were collected by using time-correlated single photon counting (TCSPC) setup from Edinburgh instrument (model: LifeSpec-II, U.K.). Herein, we described the photophysics of a hydrophilic molecule 7-(n,n׀-diethylamino) coumarin-3-carboxylic acid (7-DCCA) in the reverse micelles containing GO. It was observed that photophysics of dye is modulated in the presence of GO compared to photophysics of dye in the absence of GO inside the reverse micelles. Here we have reported the solvent relaxation and rotational relaxation time in GO containing reverse micelle and compare our work with normal reverse micelle system by using 7-DCCA molecule. Normal reverse micelle means reverse micelle in the absence of GO. The absorption maxima of 7-DCCA were blue shifted and emission maxima were red shifted in GO containing reverse micelle compared to normal reverse micelle. The rotational relaxation time in GO containing reverse micelle is always faster compare to normal reverse micelle. Solvent relaxation time, at lower w₀ values, is always slower in GO containing reverse micelle compare to normal reverse micelle and at higher w₀ solvent relaxation time of GO containing reverse micelle becomes almost equal to normal reverse micelle. Here emission maximum of 7-DCCA exhibit bathochromic shift in GO containing reverse micelles compared to that in normal reverse micelles because in presence of GO the polarity of the system increases, as polarity increases the emission maxima was red shifted an average decay time of GO containing reverse micelle is less than that of the normal reverse micelle. In GO containing reverse micelle quantum yield, decay time, rotational relaxation time, solvent relaxation time at λₑₓ=375 nm is always higher than λₑₓ=405 nm, shows the excitation wavelength dependent photophysics of 7-DCCA in GO containing reverse micelles.

Keywords: photophysics, reverse micelle, rotational relaxation, solvent relaxation

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